Treatment of fumes containing suspended solids



Feb. 12, 1957 w. A. KRlvsKY x-:rAL

TREATMENT OF FUMES CONTAINING SUSPENDED SOLIDS Filed Nov. 16, 1955 Sw, y 2v2 ..282 mm w NM. mW M m :235 EN; NRL n EN? 2v2 .n 9525 WK@ m wv-cI //u cw( IAM. .E/ u u 2o MK igw .5.3 2,6 uw M mm w wm 2o :auf o 2.23m o .y/ 1441256 3%.; :52m

nited States Patent TREATMENT OF FUMES CONTAINING SUSPENDED SOLIDS William A. Krivsky, Tonawanda, and Erich K. Modl, Niagara Falls, N. Y., assignors to Union Carbide and Carbon Corporation, a corporation of New York Application November 16, 1955, Serial No. 547,182 8 Claims. (Cl. 75-25) This invention relates to an improved method and apparatus for the treatment of gases containing suspended solids, and particularly for the treatment of gases contaminated by dust particles in the sub-micron size range.

The flue gases produced in metallurgical operations often contain dust particles in suliicient quantity to cause considerable air contamination if they are released into the atmosphere without preliminary treatment. Heretofore, dust separating equipment of the cyclone or electrostatic precipitator type has been found t be most suitable for the treatment of these contaminated gases. However, in some industrial processes, such as for example, in the oxidation of impurities in molten metal by topblowing the molten metal with oxygen or oxygen-enriched air, the fumes given off contain very small particles of metal oxides in the sub-micron particle size range. These particles are of such tine size that only expensive 4electrostatic precipitating apparatus may be employed `in the purification of the fumes. In order that metallur- :gical cleansing operations of the above type be carried out -under more favorable economic circumstances, it is necessary that a less costly manner of removing these ne :furnace flue dusts be found.

It is, therefore, a principal object of the present invenltion to overcome the aforesaid diiculties, and to provide in the treatment of gases having undesirable solid particles suspended therein, an improved method and apparatus for separating particles in all size ranges, and :at the same time provide separating equipment of good etciency and of relatively low cost.

Another object of the present invention is to provide fa novel continuous method of reducing suspended particles of carbon reducible metal oxides in a flue gas, and recovering the resulting metal values therefrom.

Yet another object of the present invention is to provide a novel system of separating finely-divided suspended :solids from a gas primarily by chemical action, whereby :the cleaned gas may be subsequently employed as a gaseons fuel.

In the drawings:

Fig. l is a simplified flow chart of the method of the present invention;

Fig, 2 is a sectional elevational view of an illustrative dust separating apparatus embodying the principles of the present invention; and

Fig. 3 is a view similar to Fig. 2, but showing a modication thereof.

For the purposes of explanation and illustration of the invention, reference is made to liue gas containing iron oxide particles in the sub-micron size range, to which the invention is particularly adapted. Referring to the ilow chart in Fig. 1, the method of the invention is carried out in a novel one-step procedure which comprises passing the iron oxide-contaminated llue gas through a heated column of coke particles. The entrained iron oxide particles are reduced to metallic iron in one portion of the column, and the ue gas is purified of suspended solids as it travels the length of the column. While the me fice chanics of the reaction which takes place in the column are not entirely understood, it is believed to involve a combination of chemical reduction and adsorption. Simultaneously with admission of the liuc gas into the coke column, steam and/or oxygen may also be introduced in suflicient quantities to control the reaction temperature in the reducing portion of the column. However, it should be understood that other means of heating and tempera ture control may be employed in the practice of the invention. Depending upon the composition of the iue gas and any gases added thereto, the resulting gas may have a heating value comparable to water gas, and will be substantially free of solids. Control of the physical state in which the reduced, metallic iron occurs may be effected by varying the ratio of steam of oxygen input into the coke column, a higher ratio of steam to oxygen being necessary to recover metallic iron in solid state rather than as a liquid.

A dust separating and fuel producing equipment 10 embodying the features of the present invention may comprise a vertical steel column or shaft 12 provided with a refractory lining or insulating jacket 14, and having one or more conventional charging chutes 16 at the top of the shaft for the introduction of carbonaceous material, such as coke. In order to achieve an eiective system for chemically reducing the very tine suspended oxide particles, the coke should be suitably sized, preferably l/ inch to 4 inches in diameter, the particle size depending upon the diameter and height of the column, in which form it also provides a suitable gas-permeable coke bed capable of liow by gravity down the shaft 10 through a stream of upwardly moving liue gas. In accordance with accepted practice of passing gas through a packed column, the colte particles should be of such size as to provide a free space between 35% and 65% of the column volume.

The dust-containing, flue gas to be treated is admitted into the reducing zone 18 of the separating equipment 10 through an inlet conduit Ztl, passing through a suitable gas-tight opening near the lower end of the shaft Wall 12 and lining 14. The gas is drawn through the coke bed 22 to the top of the column and removed through an ofi-take or exhaust pipe 24 by means of a suction blower 26.

In carrying out the invention, steam and air or oxygenenriched air may be introduced into the reducing zone 18 of the coke column to react with the coke particles. The steam and air may be charged through a separate inlet into the reducing zone, or may be mixed with the flue gas to be treated and introduced through the single conduit 20, the latter being shown and illustrated in the drawings. The combustion products thus formed mix with the line gas to provide a combustible fuel mixture having a high caloriic value. Upward passage of this fuel mixture through the coke bed results in a fuel gas product which is substantially free of suspended solids.

Control of the physical form of the metallic iron formed in the reduction zone 18 is achieved in the present invention by regulating and controlling the temperature in the reduction zone. Thus, to recover the iron in solid form, a flow of steam may be introduced into the coke column at a rate suiiicient to sustain a reaction zone temperature in said column for the reduction of the metal oxide contaminants, but at a temperature substantially below the melting range of high-carbon iron. Recovery of the metallic iron in liquid form may be effected by decreasing the ratio of steam to flue gas input into the colte column so that reaction zone temperatures substantially abovethe melting range of high carbon iron are encountered.

Illustrated in Fig. 2 is a construction which may be. used in the separation of iron oxide dusts, which is 3 adapted'to reduce themielyidivided iron oxide particles aty temperatures below the melting point of theironconstituent to be recovered. 4 A pan` disposed beneath the end of the column 1,2 As"pri`Jvide"d 'with a 'cooling water "irlt connection "3.2

*anu faa'vejrnowiip '3s to form a wafer seal suffer the column. This "A water seal cools "the rvcolumn discharge, consisting `discrete coke ash "prticle's and `mtallic 'ironpandfby conventional means discharges'it 'ovr'the Ylip 34. Thereafter, the ash and metalli'ciron rrna'y'be separatedusing conventional physical separation methods should recovery 'of 'the' iron constituentbe desired.

lathe-modification shown'in'Fig. 3, the lower end of fthe column 12 is Yterminated with a Arefractory-lined, Ai't'tom'wall'3'8 to receive "the molten discharge of the colu'nn. 'By providing tap holes 40, 42 at'diiferent levels in the shaft wall'12, slightly vabovethebottom wall 38, molten iron and slag and ash impurities, respectively, may beperiodically or-continuously tapped and removed vffroin-the separating equipment. An-obvious advantage of this vconstruction is that a low grade coke -may -be used and vthat the-metal values -may be recovered in liquid form for subsequent purposes.

The-'following example is illustrative of the beneficial results achieved in the .practice of the invention. A 100 `pound melt of pig iron was top blown, using pure oxygen, to make steel. A -typicaLfheavy reddish brown -furne, consisting mainly of iron oxide -particles of submicron size, was generated. This fume was .passed through-a six foot graphite tube furnace of 3 inchdi- -arnetervfilled with uniformly sized one inch coke parlticles, the coke column having areducing zone temperature of approximately l00O C. Using 'a Staplex `air -Sampler `to determine the solid content in the exhaust ffumes, there was no evi-dence of the slightest trace of any solid particles in the gas.

From the above it will be seen that the present invention aifords a novel continuous process and apparatus for the treatment of dust-laden gases containing carbon-reducible-metal oxide particles including the submicron particle size range, wherein -the suspended parfticles are chemically reduced and separated by passing the 'gas lthrough a column of coke particles.

It will `be understood that although the invention Vis :described in terms of the separation of iron oxide pariticles lfrornla flue gas, other important metal values such as manganese are simultaneously recovered. The Vinvention is also susceptible of application in allied fields iwhere "other carbon reducible oxide particles, particular- `ly 'of the vsub-micron size, are encountered, without departing from the spiritfand lscope of the novel concepts `of the present-invention. Furthermore, the 'reducing rcaction temperatures can be obtained by method other `than direct combustion of a coke as 4described herein, 'such as "electrical heating or gas heating.

Iis claimed is:

l. :In 'the 'artof 'recovering metal values from a liuc gas contaminated `with suspended particles of reducible metal oxides, the improvement which consists in introducing the contaminated hue gas into a heated column 'of carbonaceous particles having a sufficiently high temperature to reduce said suspended metal oxides to their 'metallic forms, and "causing the flue gas to travel the length of the column to separate said metals from said iiue gas, thereby producing a gas product substantially 'free of suspended contaminants.

2. In the art of recovering metal values from an oxygen-containing yhue gas contaminated with suspended particles of reducible metal oxides, the improvement which consists in introducing the contaminated flue gas into a :heated column of car-bonaceous material, introducing a quantity of steam sutlicient to control the reaction temperature in said column for the 'chemical reduction of said suspended Y'particles of metal 'oxides to the desired physical state, causing the ue gas to travel the length of the column toseparatesaid metals to'produce a gaseous fuel product which is substantially free of suspended contaminants.

3. In the art of purifying gas contaminated with suspended particles of iron oxide, the improvement comprising providing a column of coke particles wherein the coket-particlesare introduced into said column at the top thereof, and the contaminated Vgas is introduced into and reduced at the bottom thereof, and separated as it progresses up the column, Aintroducing into s'aidc'olu'mn a quantity of oxygen-bearing Vgases and steam'suicient to control a reaction zone temperature in said column for the (-:hernical Areduction of the Viron oxide contaminants, regulating the physical state in which the reduced iron occurs by varying `the ratio of steam to oxygen input into said column, withdrawing gaseous fuel product from the top of the coke column, and removing coke ash and iron particles Ifrom the bottom of lthe coke column. y A v 4i 4In 'the art of 'purifying gas lcontaminated with suspended particles of ironoxide, the improvement comprising providing a colu'nin of coke particles wherein the Acoke p"a'1`-'ticles are introduced into said column at the top'theref, andthe contaminated gas is introduced into `arid reduced the bottom thereofrand separated as it lprogresses up "the column, introducing into said column a quantity of steam and oxygen sutiicient to control av reaction zone temperature in said column for the reduction of the Viron oxide to liquid metal, withdrawing gaseous fuelproduct from thertop of the coke column, andrmoving coke ash and liquid iron from the bottom ofthe coke column.

5. In the art ovfpurifying gas contaminated with suspended particles of iron oxide, the improvement comprising providing a column of coke particles wherein the coke particles-are introduced intosaid column at the top thereof, and the contaminated gas is introduced into and reduced at the bottom thereof and separated as it pro,- gresses up the column, introducing with said contaminated gas a quantity of steam suflicient -to sustain a reaction zone temperature in said column for the reduction of the iron oxide to solid metal, withdrawing gaseous fuel product from the top of the coke column, and removing coke ash and iron particles from the bottom of the coke column.

6. A column vfor the purification of a tine gas contaminated with suspended particles of reducible metal oxides, comprisingla hollow shaft having at the top thereof vmeans for introducing coke particles into said column, and suction -means for withdrawing gas product substantially-free of suspended contaminating particles from the top Vof-said column, Van opening adjacent the bottom of said column for admitting the Vcontaminated flue gas in Contact with coke particles, and a discharge opening at the bottom of said column for removing coke -ash and iron particles.

7. A column for the purification of a hue gas contaminated with suspended particles ,of carbon reducible metal oxides comprising a coke-filled columnar shaft having at the top thereof, means for introducing coke particles into said column and suction means for withdrawing gas product substantially free of suspended contaminating particles, an inlet openingnear the bottom of said column for the admission of the flue gas, a reducing Zone in said coke Aadjacent said inlet opening for the reduction of said metal oxides to their metallic state, a discharge opening at the lbottom of said column for the removal of the metals and burned coke, and a separation zone in said coke between 'said-reducing zone and said suction means whereby through -the combination of said reducing and separating iones, the jiiue gas -is substantially -free of contamination and `recovery of the Ametal values -in the suspended contaminants in said tlue gas may be effected.

8. A column for the purification of flue gas contami- -na'tedwith suspended lparticles of iron oxide', comprising a coke-filled columnar shaft having at the top thereof means for introducing coke particles into said column and suction means for withdrawing gaseous fuel product substantially free of suspended contaminating particles, an inlet opening near the bottom of said column for the admission of said contaminated ue gas, an additional inlet opening for the introduction of steam and oxygen near the bottom of said column, a reducing Zone in said coke adjacent said inlet openings, a discharge opening in said column below said reducing zone for the removal of 10 the iron values in said suspended particles of iron oxide and the burned coke, and a separating zone in said coke between said reducing zone and said suction means, whereby through the combination of said reducing and separating zones purification of the ue gas may be effected, and whereby through the proportioning of the fuel to steam inputs into said coke column, a gaseous fuel product may be produced.

No references cited. 

3. IN THE ART OF PURIFYING GAS CONTAMINATED WITH SUSPENDED PARTICLES OF IRON OXIDE, THE IMPROVEMENT COMPRISING PROVIDING A COLUMN OF COKE PARTICLES WHEREIN THE COKE PARTICLES ARE INTRODUCED INTO SAID COLUMN AT THE TOP THEREOF, AND THE CONTAMINATED GAS IS INTRODUCED INTO AND REDUCED AT THE BOTTOM THEREOF, AND SEPARATED AS IT PROGRESSES UP THE COLUMN, INTRODUCING INTO SAID COLUMN A QUANTITY OF OXYGEN-BEARING GASES AND STEAM SUFFICIENT TO CONTROL A REACTION ZONE TEMPERATURE IN SAID COLUMN FOR THE CHEMICAL REDUCTION OF THE IRON OXIDE CONTAMINANTS, REGULATING THE PHYSICAL STATE IN WHICH THE REDUCED IRON OCCURS BY VARYING THE RATIO OF STEAM OF OXYGEN INPUT INTO SAID COLUMN, WITHDRAWING GASEOUS FUEL PRODUCT FROM THE TOP OF THE COKE COLUMN, AND REMOVING COKE ASH AND IRON PARTICLES FROM THE BOTTOM OF THE COKE COLUMN. 